JP6593802B2 - Inorganic coordination polymers as gelling agents - Google Patents

Description

を使用する方法（式中、Ｒ^１及びＲ^２は、互いに独立し、１つ以上のＦにより置換されることが可能であるＣ_１〜Ｃ_１０−アルキルから選択され、又は、Ｒ^１及びＲ^２は、一緒に結合しており、Ｆ及び任意にフッ素化されたＣ_１〜Ｃ_１０−アルキルから選択された１つ以上の置換基により置換されることが可能である、五員又は六員ヘテロ環基を、基−ＯＰＯ−と共に形成するＣ_２〜Ｃ_３−アルカンジイルから選択される）、
及び電気化学電池の電解質の添加剤としてそれらの使用方法に関する。さらに、本発明は、前記フルオロアルキルリン酸リチウムを含む電解質組成物、及び前記電解質組成物を含む電気化学電池に関する。 The present invention provides a lithium fluoroalkyl phosphate of general formula (I) as a gelling agent in an aprotic organic solvent,

Wherein R ¹ and R ² are independently of each other selected from C ₁ -C ₁₀ -alkyl, which can be substituted by one or more F, or R ¹ and R ² are bonded together and can be substituted by one or more substituents selected from F and optionally fluorinated C ₁ -C ₁₀ -alkyl, five-membered or six-membered Selected from C ₂ -C ₃ -alkanediyl which forms a heterocyclic group with the group —OPO—),
And their use as an additive for electrolytes in electrochemical cells. Furthermore, the present invention relates to an electrolyte composition containing the lithium fluoroalkyl phosphate, and an electrochemical cell containing the electrolyte composition.

  There is still a growing interest in storing electrical energy. Efficient storage of electrical energy produces electrical energy when advantageous and allows the use of electrical energy when necessary. Currently, lithium ion batteries, often referred to as lithium ion batteries, are widely used to provide electrical energy, especially in portable devices such as notebook computers and mobile phones, and are also used in electric mobility. ing. Lithium ion batteries offer higher energy densities than batteries based on lead or lower activity heavy metals.

  Electrochemical cells, such as lithium ion cells, include an electrolyte composition that includes a cathode, an anode, and a conductive salt for ion exchange between the cathode and the anode. Various electrolyte compositions are known and most commonly used are liquid electrolytes, but solid electrolytes and gel electrolytes are also used.

  A solid electrolyte is a substance that conducts electricity by ion diffusion. Suitable materials include, for example, polymers such as polyethylene oxide or polyvinylidene fluoride. The polymer is mixed with a conductive salt. Polymer electrolytes exhibit mechanical stability and low volatility properties, but have low electrical conductivity. In general, the liquid electrolyte is composed of one or more solvents, conductive salts solvating thereto, and any additional additives. In general, liquid electrolytes exhibit good ionic conductivity, but electrochemical cells must be sealed to avoid electrolyte loss. The gel electrolyte is in the middle of the above two types, and relates to a solid substance such as a polymer and a solid substance that forms a gel, and is generated by a liquid solvent containing a conductive salt. Usually only a small amount of liquid solvent is required to produce a gel. Compared to a solid electrolyte, a large amount of solvent results in an increase in the electrical conductivity of the gel electrolyte. In addition, the solvent is fixed in the gel and has a lower risk of solvent leakage than the liquid electrolyte.

Currently, development is progressing towards higher voltage batteries that provide higher energy densities in the lithium ion battery area. High voltage cathode materials such as LiCoPO ₄ and manganese-containing spinels exhibit voltages in excess of 4.5V relative to Li / Li ⁺ . The electrolyte used in combination with these materials must exhibit good electrochemical stability and good compatibility with the electrode material to give the electrochemical cell a long life. These requirements are also sought for solvents, conductive salts, and other usable components of the electrolyte composition that are not consumed over the life of the electrochemical cell. Furthermore, the requirements for good electrical conductivity and high safety of the electrolyte composition must be met.

  An object of the present invention is to provide an electrolyte composition for an electrochemical cell, in particular, a lithium ion battery exhibiting good electrical conductivity, safety characteristics and good electrochemical stability at a high voltage. Furthermore, it is an object of the present invention to provide an electrochemical cell, in particular a lithium ion battery exhibiting good safety characteristics and a long life, in particular an electrochemical cell having a high energy density.

（式中、Ｒ^１及びＲ^２は、互いに独立し、１つ以上のＦにより置換されることが可能であるＣ_１〜Ｃ_１０−アルキルから選択され、
又は、
Ｒ^１及びＲ^２は、一緒に結合しており、Ｆ及び任意にフッ素化されたＣ_１〜Ｃ_１０−アルキルから選択された１つ以上の置換基により置換されることが可能である、五員又は六員ヘテロ環基を、基−ＯＰＯ−と共に形成するＣ_２〜Ｃ_３−アルカンジイルから選択される）
の化合物の使用により達成される。 For this purpose, the general formula (I),

Wherein R ¹ and R ² are selected from C ₁ -C ₁₀ -alkyl, independently of one another, which can be substituted by one or more F;
Or
R ¹ and R ² are bonded together and can be substituted with one or more substituents selected from F and optionally fluorinated C ₁ -C ₁₀ -alkyl. Selected from C ₂ -C ₃ -alkanediyl, which forms a membered or six-membered heterocyclic group with the group —OPO—)
Is achieved by the use of

This purpose is also
(I) at least one aprotic organic solvent,
(Ii) at least one compound of general formula (I),
(Iii) at least one conductive salt different from the compound of general formula (I), and
(Iv) optionally at least one further additive;
By the electrolyte composition (A) containing
Moreover, it is achieved by an electrochemical cell containing the electrolyte composition (A).

  The compound of general formula (I) produces a coordination polymer by the addition of an organic aprotic solvent such as carbonate. It is understood that the low molecular weight compound of general formula (I) produces a Li metal complex in a solvent that is added by a coordination bond that results in a large molecule called a coordination polymer. Formation of a coordination polymer with a low molecular weight compound has the effect of a gelling agent in an aprotic organic solvent. The presence of only a small amount of a compound of general formula (I) in an aprotic organic solvent is sufficient to obtain a gel produced by a network of coordination polymers filled with solvent (s). . It is possible to use aprotic organic solvents and solvent mixtures such as carbonates and ethers commonly used in electrochemical cell electrolyte compositions. Conventional conductive salts are easily added to the gel. As a result, these gels provide a good basis for electrolyte compositions that have a lower risk of solvent leakage. Since no harmful ions such as Na + or transition metal ions are introduced into the battery, the use of the compound of general formula (I) as a gelling agent is that lithium ions such as lithium ion batteries or lithium sulfur batteries are anodes. It is particularly advantageous for electrochemical cell electrolyte compositions used for ion transfer between the cathode and the cathode. The compound of the general formula (I) is electrochemically stable at 5 V or less.

Due to the inorganic moiety, the coordination polymer produced by the compound of the general formula (I) and the compound of the general formula (I) is conventionally used when the substituents R ¹ and / or R ² are substituted with F. Lower flammability than other organic polymers. It also provides improved flame retardancy of the electrolyte composition.

  The electrolyte composition (A) of the present invention contains at least one aprotic organic solvent (i), preferably at least two aprotic organic solvents (i). According to one embodiment, the electrolyte composition (A) may contain 10 or less aprotic organic solvents (i).

Preferably, at least one aprotic organic solvent (i) is
(A) cyclic and acyclic organic carbonates, which may be partially halogenated,
(B) may be partially halogenated, di _-C 1 _{-C 10} - alkyl ethers,
(C) may be partially halogenated, di _-C 1 -C ₄ - alkyl _-C 2 -C ₆ - alkylene ether and polyethers,
(D) a cyclic ether, which may be partially halogenated,
(E) cyclic and acyclic acetals and ketals, which may be partially halogenated,
(F) orthoesters, which may be partially halogenated,
(G) cyclic and acyclic carboxylic esters that may be partially halogenated,
(H) cyclic and acyclic sulfones, which may be partially halogenated,
(I) cyclic and acyclic nitriles and dinitriles, which may be partially halogenated, and
(J) an ionic liquid, which may be partially halogenated,
Selected from.

More preferably, at least one aprotic organic solvent (i) is cyclic and acyclic organic carbonates (a), di _-C 1 _{-C 10} - alkyl ether (b) di _-C 1 -C ₄ - Selected from alkyl-C ₂ -C ₆ -alkylene ethers and polyethers (c) and cyclic ethers (d), even more preferably, at least one aprotic organic solvent (i) is cyclic and acyclic Selected from organic carbonates (a), most preferably at least one aprotic organic solvent (i) is at least two aprotic organic solvents selected from cyclic and acyclic organic carbonates (a) It is a mixture of (i), particularly preferably the at least one aprotic organic solvent (i) is a mixture of at least one cyclic organic carbonate and at least one acyclic organic carbonate. It is.

  The aprotic organic solvents (a) to (j) may be partially halogenated, for example, partially fluorinated, partially chlorinated or partially brominated, preferably May be partially fluorinated. The term “partially halogenated” means that one or more H of an individual molecule is replaced with a halogen atom (eg, F, Cl or Br). The at least one solvent (i) may be selected from partially halogenated and non-halogenated aprotic organic solvents (a) to (j), in other words, the electrolyte composition is partially halogenated A mixture of halogenated and non-halogenated aprotic organic solvents may be included.

（式中、Ｒ^ａ、Ｒ^ｂ及びＲ^ｃは、異なり又は同一であり、互いに独立し、水素、Ｃ_１〜Ｃ_４−アルキル、好ましくはメチル、Ｆ、及び１つ以上のＦに置換されるＣ_１〜Ｃ_４−アルキル、例えばＣＦ_３から選択される）
の環状有機炭酸塩である。 Examples of suitable organic carbonates (a) are those of the general formula (a1), (a2) or (a3),

Wherein R ^a , R ^b and R ^c are different or the same and are independent of each other and substituted with hydrogen, C ₁ -C ₄ -alkyl, preferably methyl, F, and one or more F. C ₁ -C ₄ -alkyl, eg selected from CF ₃ )
The cyclic organic carbonate.

The term “C ₁ -C ₄ -alkyl” refers to methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec. -Butyl, and tert. -Means containing butyl.

Preferred cyclic organic carbonates (a) are those of general formula (a1), (a2) or (a3) where R ^a , R ^b and R ^c are H. Examples include ethylene carbonate, vinylene carbonate and propylene carbonate. A preferred cyclic organic carbonate (a) is ethylene carbonate. Further preferred cyclic organic carbonates (a) are difluoroethylene carbonate (a4) and monofluoroethylene carbonate (a5).

  Examples of suitable acyclic organic carbonates (a) are dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and mixtures thereof.

  In one embodiment of the invention, the electrolyte composition (A) comprises an acyclic organic carbonate (a) and a cyclic organic carbonate in a mass ratio of 1:10 to 10: 1, preferably 3: 1 to 1: 1. Contains a mixture with salt (a).

Examples of suitable acyclic di-C ₁ -C ₁₀ -alkyl ethers (b) are dimethyl ether, ethyl methyl ether, diethyl ether, diisopropyl ether and di-n-butyl ether.

Examples of di-C ₁ -C ₄ -alkyl-C ₂ -C ₆ -alkylene ethers (c) are 1,2-dimethoxyethane, 1,2-diethoxyethane, diglyme (diethylene glycol dimethyl ether), triglyme (triethylene). Glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether) and diethylene glycol diethyl ether.

Examples of suitable polyethers (c) are polyalkylene glycols, preferably poly-C ₁ -C ₄ -alkylene glycols, especially polyethylene glycol. The polyethylene glycol may contain 20 mol% or less of one or more copolymerized forms of ethylene glycol. Preferably, the polyalkylene glycol is a dimethyl- or diethyl-end-capped polyalkylene glycol. The molecular weight M _W of suitable polyalkylene glycols and particularly preferred polyethylene glycol may be at least 400 g / mol. The molecular weight _{M W} of suitable polyalkylene glycols and particularly preferred polyethylene glycol, 5 000 000 g / mol or less, preferably may be less than or equal to 2,000,000 g / mol.

  Examples of suitable cyclic ethers (d) are tetrahydrofuran and 1,4-dioxane.

  Examples of suitable acyclic acetals (e) are 1,1-dimethoxymethane and 1,1-diethoxymethane. Examples of suitable cyclic acetals (e) are 1,3-dioxane and 1,3-dioxolane.

Examples of suitable orthoesters (f) are tri-C ₁ -C ₄ -alkoxymethanes, in particular trimethoxymethane and trieximethane. Examples of suitable cyclic orthoesters (f) are 1,4-dimethyl-3,5,8-trioxabicyclo [2.2.2] octane and 4-ethyl-1-methyl-3,5,8- Trioxabicyclo [2.2.2] octane.

  Examples of suitable acyclic carboxylic acid esters (g) are carboxylic acid esters such as ethyl acetate, methyl butanoate, and dimethyl 1,3-propanoate. An example of a suitable cyclic carboxylic acid ester is γ-butyrolactone.

  Examples of suitable cyclic and acyclic sulfones are ethyl methyl sulfone, dimethyl sulfone and tetrahydrothiophene-S, S-dioic acid.

  Examples of suitable cyclic and acyclic nitriles and dinitriles (i) are adepositonitrile, acetonitrile, propionitrile and butyronitrile.

  The water content of the electrolyte composition of the present invention is preferably less than 100 ppm, more preferably less than 50 ppm, and most preferably less than 30 ppm, based on the weight of the electrolyte composition. The water content can be measured, for example, by Karl Fischer titration as described in detail in DIN 51777 or ISO 760: 1978.

  The HF content of the electrolyte composition of the present invention is preferably less than 60 ppm, more preferably less than 40 ppm, and most preferably less than 20 ppm based on the mass of the electrolyte composition. The HF content can be measured by potentiometric titration or potential graph titration.

（式中、Ｒ^１及びＲ^２は、互いに独立し、１つ以上のＦにより置換されることが可能であるＣ_１〜Ｃ_１０−アルキルから選択され、
又は、Ｒ^１及びＲ^２は、一緒に結合しており、Ｆ及び任意にフッ素化されたＣ_１〜Ｃ_１０−アルキルから選択された１つ以上の置換基により置換されることが可能である、五員又は六員ヘテロ環基を、基−ＯＰＯ−と共に形成するＣ_２〜Ｃ_３−アルカンジイルから選択される）
の化合物を含む。 The electrolyte composition (A) of the present invention contains at least one general formula (I) as component (ii).

Wherein R ¹ and R ² are selected from C ₁ -C ₁₀ -alkyl, independently of one another, which can be substituted by one or more F;
Or, R ¹ and R ² are bonded together and can be substituted with one or more substituents selected from F and optionally fluorinated C ₁ -C ₁₀ -alkyl. , Selected from C ₂ -C ₃ -alkanediyl which forms a 5- or 6-membered heterocyclic group with the group —OPO—
Of the compound.

（式中、Ｒ、Ｒ^ｉ、Ｒ^ｉｉ、Ｒ^ｉｉｉ、Ｒ^ｉｖ及びＲ^ｖは、互いに独立し、Ｈ、Ｆ及び任意にフッ素化されたＣ_１〜Ｃ_１０−アルキルから選択される）
である。 Compounds of general formula (I) wherein R ¹ and R ² are bonded together and selected from C ₂ -C ₃ -alkanediyl which together with the group —OPO— form a 5- or 6-membered heterocyclic group Examples of

Wherein R, R ⁱ , R ⁱⁱ , R ⁱⁱⁱ , R ^iv and R ^v are independent of each other and are selected from H, F and optionally fluorinated C ₁ -C ₁₀ -alkyl.
It is.

Preferably, ^{R 1} and ^{R 2} are, independently of one another, _C 1 is capable of being substituted by one or more F -C ₄ - is selected from alkyl, or, ^{R 1} and ^{R 2} forming combined and it has, and fluorinated C ₁ -C 10 in F and optionally together _- is selected from the alkanediyl - C ₂ is capable of being substituted by one or more substituents selected from alkyl.

The term “C ₁ -C ₁₀ -alkyl” as used herein means a straight or branched saturated hydrocarbon having 1 to 10 carbon atoms and having a free valence of 1; For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl, iso-hexyl, 2-ethylhexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl and the like. _Preferably, C 1 _{~C 4} - alkyl.

The term “C ₂ -C ₃ -alkanediyl” as used herein refers to a saturated hydrocarbon having 2 to 3 carbon atoms and having a free valence of 2. C ₂ -C ₃ - alkanediyl is, for example, _-CH 2 CH ₂ - containing - and _{-CH 2 CH} 2 _CH 2.

At least one compound of general formula (I) is preferably substituted at least one of R ¹ and R ² by at least one F, more preferably at least one of R ¹ and R ² is substituted by at least two F And most preferably selected from compounds of general formula (I) in which at least one of R ¹ and R ² is substituted by at least 3 F. Particularly preferably, at least one of R ¹ and R ² comprises at least one CF ³ — group.

According to one embodiment of the present invention, at least one compound of general formula (I) is selected from general formula (1) wherein R ¹ and R ² are independently of one another and optionally fluorinated C ₁ -C ₄ -alkyl. Selected from compounds of I). Preferably at least one of R ¹ and R ² is substituted by at least one F, more preferably at least one of R ¹ and R ² is substituted by at least two F, and most preferably at least one of R ¹ and R ² Are replaced by at least three Fs. Particularly preferably, at least one of R ¹ and R ² comprises at least one CF ³ — group.

According to another embodiment, the at least one compound of general formula (I) is selected from F 1 and optionally fluorinated C ₁ -C ₁₀ -alkyl, wherein R ¹ and R ² are bonded together. A 5- or 6-membered heterocyclic group that can be substituted by one or more of the substituents selected is selected from C ₂ -alkanediyl that forms with the group —OPO—. The C ₂ - alkanediyl, preferably comprises at least one F, more preferably at least two F, still more preferably at least three F. Particularly preferably, the five-membered heterocycle contains at least one CF ³ — group.

Preferred compounds of the general formula (I) are LiOOP (OCH ₂ CF ₃ ) ₂ , LiOOP (OCH (CF ₃ ) ₂ ) ₂ , LiOOP (On-C ₄ F ₉ ) ₂ and LiOOP (OC (CF ₃ ) ₃ ). ₂ .

Different processes are known for the preparation of optionally fluorinated lithium alkyl phosphate compounds of general formula (I). One idea is to produce the corresponding (fluoro) alkyl phosphoric acid by reacting with a deprotonating agent such as lithium hydroxide or butyl lithium. The preparation of the corresponding (fluoro) alkyl phosphate is described, for example, in Mahmood, T .; And Shreeve, J .; M.M. Inorg. Chem. 25, pages 3830-3837 (1986). Another possibility is to react individual lithium (fluoro) alkoxides with phosphorus pentoxide. Another subject of the present invention is to react LiOR ¹ , LiOR ² and / or LiOR ¹ R ² OLi with phosphorus pentoxide, R ¹ and R ² are defined as above and R ¹ R ² Are selected from C ₂ -C ₃ -alkanediyl bonded together and capable of being substituted by one or more F and / or optionally fluorinated C ₁ -C ₁₀ -alkyl. This is the part. LiOR ¹ , LiOR ² and / or LiOR ¹ R ² OLi are easily produced by reacting the corresponding alcohol with a deprotonating agent such as lithium hydroxide or butyl lithium. In general, LiOR ¹ , LiOR ² and / or LiOR ¹ R ² OLi and phosphorus pentoxide are reacted in the presence of an aprotic solvent such as a carbonate such as dimethyl carbonate. Generally, the reaction temperature exceeds room temperature, for example, a suitable temperature range is 50-120 ° C. In addition, lithium bis- (2,2,2-trifluoroethyl) phosphate directly reacts with the corresponding alcohol by phosphorus pentoxide deprotonated with a deprotonating agent such as lithium hydroxide or butyl lithium. Manufactured.

  Generally, the electrolyte composition (A) comprises at least 0.01 mol / L of at least one compound of general formula (I). In general, the maximum concentration of at least one compound of general formula (I) is 5 mol / L. When the compound of general formula (I) is used in the electrolyte composition as a gelling agent, the concentration of at least one compound of general formula (I) is preferably based on the total volume of the electrolyte composition (A) Is 0.1 to 5 mol / L, more preferably 0.15 to 3 mol / L, and most preferably 0.2 to 2 mol / L.

  The small molecule lithium fluoroalkyl phosphate of general formula (I) produces a coordination polymer in solvent that results in a gel consisting of a network of coordination polymers and solvent molecules distributed within the overall network of polymers. The gel has finite yield stress and exhibits both elasticity and viscosity. This is reflected by the development of storage modulus G 'and loss modulus G "measured by rheological oscillation experiments. In a deformation sweep, the storage elastic modulus G 'is larger than the loss elastic modulus in small deformation, which is rather close to a solid phase material. This indicates that the gel is more like a liquid because it changes with higher deformation values. In a frequency sweep experiment with small deformations, the storage modulus G 'of the gel is greater than the loss modulus G "and at least both proceed in parallel in an ideal gel. According to a preferred embodiment of the present invention, the electrolyte composition (A) is a gel electrolyte.

Furthermore, the electrolyte composition (A) of the present invention contains a conductive salt (iii) different from at least one compound of the general formula (I). The electrolyte composition (A) serves as a medium for conducting ions involved in the electrochemical reaction performed in the electrochemical cell. In general, the conductive salt (s) (iii) present in the electrolyte are solvated in the aprotic organic solvent (s) (i). Preferably, the conductive salt (iii) is a lithium ion containing a conductive salt. Preferably, the conductive salt is
_{Li [F 6-x P (} C y F 2y + 1) x] ( where, x is an integer in the range of Less than six, y is an integer ranging from 1 to 20);
Li [B (R ^I ) ₄ ], Li [B (R ^I ) ₂ (OR ^II O)] and Li [B (OR ^II O) ₂ ] (wherein each R ^I is independent of each other and F _{, Cl, Br, I, C} 1 ~C 4 - _alkaline, C 2 _{~C 4} - _alkenyl, C 2 _{~C 4} - alkynyl, _OC 1 ~C ₄ - alkaline, _OC 2 ~C ₄ - alkenyl and _OC 2 ~ Selected from C ₄ -alkynyl, wherein alkali, alkenyl and alkynyl may be substituted by one or more OR ^III , R ^III is C ₁ -C ₆ -alkali, C ₂ -C ₆ -alkenyl and C ₂ -C Selected from ₆ -alkynyl and
(OR ^II O) is a divalent group derived from 1,2- or 1,3-diol, 1,2- or 1,3-dicarboxylic acid, or 1,2- or 1,3-hydroxycarboxylic acid And the divalent group forms a 5- or 6-membered ring with the central B-atom by both oxygen atoms);
LiClO ₄ ; LiAsF ₆ ; LiCF ₃ SO ₃ ; Li ₂ SiF ₆ ; LiSbF ₆ ; LiAlCl ₄ , lithium tetrafluoro (oxalate) lithium phosphate; lithium oxalate; LiN (SO ₂ F) ₂ ;
General formula Li [Z (CnF _{2n + 1} SO ₂ ) _m ] (where m and n are
When Z is selected from oxygen and sulfur, m is 1.
When Z is selected from nitrogen and phosphorus, m is 2.
When Z is selected from carbon and silicon, m is 3;
n is an integer in the range of 1-20,
Defined)),
Selected from the group consisting of

Suitable 1,2- or 1,3-diols that generate divalent groups (OR ^II O) are aliphatic or aromatic, eg, one or more F and / or at least one 1,2-dihydroxybenzene, propane-1,2-optionally substituted with linear or branched non-fluorinated, partially fluorinated or fully fluorinated C ₁ -C ₄ -alkali groups It may be selected from diols, butane-1,2-diol, propane-1,3-diol, butane-1,3-diol, cyclohexyl-trans-1,2-diol and naphthalene-2,3-diol. Examples of such 1,2- or 1,3-diol include 1,1,2,2-tetra (trifluoromethyl) -1,2-ethanediol.

The term “fully fluorinated C ₁ -C ₄ -alkali group” means that the H-atoms of all alkyl groups are replaced by F.

Suitable 1,2- or 1,3-dicarboxylic acids that generate divalent groups (OR ^II O) are aliphatic or aromatic, such as oxalic acid, malonic acid (propane-1,3-dicarboxylic acid) Phthalic acid or isophthalic acid, preferably oxalic acid. The 1,2- or 1,3-dicarboxylic acid optionally has one or more F and / or at least one linear or branched, non-fluorinated, partially fluorinated or fully fluorinated. The substituted C ₁ -C ₄ -alkali group is substituted.

Suitable 1,2- or 1,3-hydroxycarboxylic acids that form divalent groups (OR ^II O) are aliphatic or aromatic, eg, one or more F, and / or at least one straight chain. not fluorinated chain or branched, partially fluorinated is or completely fluorinated C ₁ -C 4 _- salicylic acid, which is optionally substituted by an alkali base, tetrahydrophthalic acid, a malic acid and 2-hydroxy acetic acid May be. Examples of such 1,2- or 1,3-hydroxycarboxylic acids include 2,2-bis (trifluoromethyl) -2-hydroxy-acetic acid.

Examples of Li [B (R ^I ) ₄ ], Li [B (R ^I ) ₂ (OR ^II O)] and Li [B (OR ^II O) ₂ ] include LiBF ₄ , lithium difluorooxalatoborate and Examples include lithium dioxalatoborate.

Preferably, the at least one conductive salt (iii) is LiBF ₄ , lithium difluorooxalatoborate, lithium dioxalatoborate, Li [N (FSO ₂ ) ₂ ], Li [N (CF ₃ SO ₂ ) ₂ ]. , LiClO ₄ , LiPF ₆ and LiPF ₃ (CF ₂ CF ₃ ) ₃ , more preferably selected from LiPF ₆ , LiBF ₄ and LiPF ₃ (CF ₂ CF ₃ ) ₃ , and even more preferably a conductive salt (iii) Is selected from LiPF ₆ and LiBF ₄ , most preferably the conductive salt (iii) is LiPF ₆ .

  Generally, at least one conductive salt (iii) is present at a minimum concentration of at least 0.1 mol / L. In general, the maximum concentration is 2 mol / L based on the total volume of the electrolyte composition.

  The electrolyte composition (A) is composed of vinylene carbonate and its derivatives, vinyl ethylene carbonate and its derivatives, methyl ethylene carbonate and its derivatives, (bisoxalato) lithium borate, difluoro (oxalato) lithium borate, tetrafluoro (oxalato) phosphoric acid Lithium, lithium oxalate, 2-vinylpyridine, 4-vinylpyridine, cyclic exo-methylene carbonate, sultone, cyclic and acyclic sulfonates, cyclic and acyclic sulfites, organic esters of inorganic acids, at least 36 at 1 bar Acyclic and acyclic alkanes having boiling points of ° C, and optionally halogenated cyclic and acyclic sulfonylimides, optionally halogenated cyclic and acyclic phosphate esters, optionally halogenated cyclic and acyclic phosphines, optional Halogenated Cyclic and acyclic phosphites, optionally halogenated cyclic and acyclic phosphazenes, optionally halogenated cyclic and acyclic silylamines, optionally halogenated cyclic and acyclic halogenated esters, optionally halogenated cyclic And at least one additive (iv) selected from the group consisting of acyclic amides, optionally halogenated cyclic and acyclic anhydrides, ionic liquids, and optionally aromatic compounds containing halogenated heterocycles May be included. Preferably, additive (iv) is selected to be different from the compound selected from the conductive salt (iii) present in the individual electrolyte composition (A). Preferably, additive (iv) is also different from said at least one organic aprotic solvent (i) present in the individual electrolyte composition (A).

（式中、
Ｒは、Ｈ、Ｃ_１−〜Ｃ_６−アルキル、Ｃ_２−〜Ｃ_６−アルケニル及びフェニル、好ましくはメチル、エチル及びプロピルを示す；
Ｒ^Ａは、−（ＣＨ_２）_ｓ−Ｏ−Ｃ（Ｏ）−Ｒ、−（ＣＨ_２）_ｓ−Ｃ（Ｏ）−ＯＲ, −（ＣＨ_２）_ｓ−Ｓ（Ｏ）_２−ＯＲ、−（ＣＨ_２）_ｓ−Ｏ−Ｓ（Ｏ）_２−ＯＲ、−（ＣＨ_２）_ｓ−Ｏ−Ｃ（Ｏ）−ＯＲ、−（ＣＨ_２）_ｓ−ＨＣ＝ＣＨ−Ｒ、−（ＣＨ_２）_ｓ −ＣＮ、

（式中、各ＣＨ_２基が、Ｏ、Ｓ又はＮＲに代替されてもよく、ｓが、１〜８、好ましくは１〜３である）
を示す；
Ｘ^Ａは、ＣＨ_２、Ｏ、Ｓ又はＮＲ^Ｂを示す；
Ｒ^Ｂは、Ｈ、Ｃ_１−〜Ｃ_６−アルキル、Ｃ_２−〜Ｃ_６−アルケニル、フェニル、及び、ｓが１〜８、好ましくは１〜３である−（ＣＨ_２）_ｓ−ＣＮを示す；好ましくは、Ｒ^Ｂは、メチル、エチル、プロピル又はＨである）
のカチオン群から選択されたカチオンを示し、
［Ｌ］⁻が、ＢＦ_４ ⁻、ＰＦ_６ ⁻、［Ｂ（Ｃ_２Ｏ_４）_２］⁻、［Ｆ_２Ｂ（Ｃ_２Ｏ_４）］⁻、［Ｎ（Ｓ（Ｏ）_２Ｆ）_２］⁻、［Ｆ_ｐＰ（Ｃ_ｑＦ_２ｑ＋１）_６−ｐ］⁻、［Ｎ（Ｓ（Ｏ）_２Ｃ_ｑＦ_２ｑ＋１）_２］⁻、［（Ｃ_ｑＦ_２ｑ＋１）_２Ｐ（Ｏ）Ｏ］⁻、［Ｃ_ｑＦ_２ｑ＋１Ｐ（Ｏ）Ｏ_２］^２−、［ＯＣ（Ｏ）Ｃ_ｑＦ_２ｑ＋１］⁻、［ＯＳ（Ｏ）_２ＣｑＦ_２ｑ＋１］⁻；［Ｎ（Ｃ（Ｏ）Ｃ_ｑＦ_２ｑ＋１）_２］⁻；［Ｎ（Ｃ（Ｏ）Ｃ_ｑＦ_２ｑ＋１）（Ｓ（Ｏ）_２Ｃ_ｑＦ_２ｑ＋１）］⁻；［Ｎ（Ｃ（Ｏ）Ｃ_ｑＦ_２ｑ＋１）（Ｃ（Ｏ））Ｆ］⁻；［Ｎ（Ｓ（Ｏ）_２Ｃ_ｑＦ_２ｑ＋１）（Ｓ（Ｏ）_２Ｆ）］⁻；［Ｃ（Ｃ（Ｏ）Ｃ_ｑＦ_２ｑ＋１）_３］⁻及び［Ｃ（Ｓ（Ｏ）_２Ｃ_ｑＦ_２ｑ＋１）_３Ｎ（ＳＯ_２ＣＦ_３）_２］⁻、
（式中、ｐが０〜６の範囲の整数であり、ｑが１〜２０の範囲の整数であり、好ましくはｑが１〜４の範囲の整数である）
の群から選択されたアニオンを示す。 Preferred ionic liquids of the present invention are selected from ionic liquids of the formula [K] ⁺ [L] ⁻ , wherein [K] ⁺ is preferably of general formula (II) to (IX)

(Where
R represents H, C _1-to C ₆ -alkyl, C _2-to C ₆ -alkenyl and phenyl, preferably methyl, ethyl and propyl;
R ^A is — (CH ₂ ) _s —O—C (O) —R, — (CH ₂ ) _s —C (O) —OR, — (CH ₂ ) _s —S (O) ₂ —OR, — _{(CH 2) s -O-S} (O) 2 -OR, - (CH 2) s -O-C (O) -OR, - (CH 2) s -HC = CH-R, - (CH 2) _s- CN,

(Wherein each CH ₂ group may be replaced by O, S or NR, and s is 1 to 8, preferably 1 to 3)
Indicates;
X ^A represents CH ₂ , O, S or NR ^B ;
R ^B _{is, H,} C 1 _{-~C 6} - _alkyl, C 2 _{-~C 6} - alkenyl, phenyl, and, s is 1-8, is preferably 1 to 3 - a _{(CH 2)} s -CN shown; preferably, ^{R B} is methyl, ethyl, propyl or H)
A cation selected from the cation group of
[L] ⁻ is BF ₄ ⁻ , PF ₆ ⁻ , [B (C ₂ O ₄ ) ₂ ] ⁻ , [F ₂ B (C ₂ O ₄ )] ⁻ , [N (S (O) ₂ F) _{2 ^{] -, [F p P (}} C q F 2q + 1) 6-p] -, [N (S (O) 2 C q F 2q + 1) 2] -, [(C q F 2q + 1) 2 P (O) O] ⁻ , [C _q F _{2q + 1} P (O) O ₂ ] ²⁻ , [OC (O) C _q F _{2q + 1} ] ⁻ , [OS (O) ₂ CqF _{2q + 1} ] ⁻ ; [N (C (O) C _q F ^{_{2q + 1) 2] -;}} [N (C (O) C q F 2q + 1) (S (O) 2 C q F 2q + 1)] -; [N (C (O) C q F 2q + 1) (C (O)) ^{_{F] -; [N (S}} (O) 2 C q F 2q + 1) (S (O) 2 F)] -; [C (C (O) C q F 2q + 1) 3] - , and [C (S (O _{2 C q F 2q + 1)} 3 N (SO 2 CF 3) 2] -,
(Wherein p is an integer in the range of 0-6, q is an integer in the range of 1-20, and preferably q is an integer in the range of 1-4)
An anion selected from the group of

Preferred ionic liquids used as additives (iv) are those of the formula [K] [L] (wherein [K] is a general formula wherein X is CH ₂ and s is an integer in the range of 1 to 3). Selected from the pyrrolidinium cations of (II), [L] is BF ₄ ⁻ , PF ₆ ⁻ , [B (C ₂ O ₄ ) ₂ ] ⁻ , [F ₂ B (C ₂ O ₄ )] ⁻ , [N (S (O) ₂ F) ₂ ] ⁻ , [N (SO ₂ C ₂ F ₅ ) ₂ ² ] ⁻ , [F ₃ P (C ₂ F ₅ ) ₃ ] ⁻ and [F ₃ P (C ₄ F ₉ ) ₃ ] ^- )).

  When one or more additional additives (iv) are present in the electrolyte composition (A), the total concentration of the additional additives (iv) is at least 0.001 based on the total mass of the electrolyte composition (A). It is mass%, Preferably it is 0.005-5 mass%, More preferably, it is 0.01-2 mass%.

  The electrolyte composition (A) provides a mixture of at least one solvent (i), at least one conductive salt (iii) and optionally one or more additives (iv), having the general formula ( It may be produced by adding the compound of I) and mixing all the components. In some cases, it is useful to treat the solution in an ultrasonic bath to ensure gel uniformity.

  A further object of the invention is a process for using a compound of general formula (I) as defined in detail above, including preferred embodiments, as a gelling agent in an aprotic organic solvent or solvent mixture. Typical aprotic organic solvents are those described in detail above, including preferred embodiments, as aprotic organic solvent (i). Preferred aprotic organic solvent (s) are selected from cyclic and acyclic organic carbonates. Generally, the compound of general formula (I) is 0 based on the total volume of the composition containing the aprotic organic solvent (s) and the compound (s) of general formula (I). Use at least one compound of general formula (I) as a gelling agent at a concentration in the range of 1-5 mol / L, more preferably 0.15-3 mol / L, most preferably 0.2-2 mol / L Is done. Preferably, the compound of general formula (I) is used as a gelling agent in non-aqueous electrolyte compositions containing an aprotic organic solvent (s). A further object of the present invention is to add an aprotic organic solvent or an aprotic compound by adding at least one compound of general formula (I) to an aprotic organic solvent or a mixture of aprotic organic solvents as described above. It is the method of gelatinizing the mixture of an organic solvent. The term “gelling” induces gelation of a mixture of a protic organic solvent or an aprotic organic solvent to produce a mixture of a protic organic solvent or an aprotic organic solvent and at least one general formula ( A gel is obtained comprising a compound of I) and optionally further compounds such as conductive salts and additives such as the conductive salts (iii) and additives (iv) described above.

  Another object of the invention is a method of using at least one compound of general formula (I) as an additive for electrolytes for electrochemical cells. In general, the compound of the general formula (I) is used at a concentration within the above range with respect to the electrolyte composition (A) of the present invention.

Another object of the present invention is an electrochemical cell comprising an electrolyte composition (A) as described in detail above. In particular, the electrochemical cell is
(A) the above electrolyte composition,
(B) at least one cathode comprising at least one cathode active material; and
(C) at least one anode comprising at least one anode active material;
including.

  Preferably, the electrochemical cell of the present invention is a lithium cell, in other words, an electrochemical cell in which the anode contains lithium metal or lithium ions somewhere during the value charge / discharge of the cell. The anode can include lithium metal or a lithium metal alloy (a lithium-containing compound or a material that incorporates lithium ions), such as a lithium ion battery, a lithium / sulfur battery, or a lithium / selenium sulfur battery. Preferably, the electrochemical battery is a lithium ion secondary battery or a lithium sulfur battery.

  Lithium / sulfur batteries include a sulfur-containing material as a cathode active material. In general, sulfur is a conductive material and particularly preferably carbonaceous conductivity such as carbon black, graphite, expanded graphite, graphene, carbon fiber, carbon nanotube, activated carbon, carbon produced by heat treatment of cork or pitch. It exists as a mixture or complex with the substance. It is also possible to use other conductive materials such as metal powders, metal flakes, metal compounds or mixtures thereof. Mixtures or composites containing sulfur are often made from elemental sulfur or a polymer containing sulfur.

  Generally, the lithium anode includes lithium metal and / or a lithium metal alloy. In lithium / sulfur batteries, lithium-aluminum alloys, lithium-tin alloys, Li-Mg alloys and Li-Ag alloys may be used.

  Preferably, the electrochemical cell is a secondary lithium ion electrochemical cell or a lithium sulfur battery, in other words, a cathode including a cathode active material capable of reversibly occluding and releasing lithium ions, and reversible lithium ions. A secondary lithium ion electrochemical cell including an anode containing an anode active material that can be occluded and released. Within the scope of the present invention, “secondary lithium ion electrochemical cells” and “(secondary) lithium ion cells” are used alternately.

  Preferably, the at least one cathode active material comprises a material selected from lithiated phosphate transition metals and transition metal oxides that insert lithium ions and capable of occluding and releasing lithium ions.

An example of a lithiated phosphate transition metal is LiCoPO ₄ , and an example of a transition metal oxide that inserts lithium ions is the general formula (X) Li _{(1 + z)} [Ni _a Co _b Mn _c ] _{(1-z) 2} O _{2 + e} (wherein z is 0 to 0.3; a, b and c are the same or different and each is 0 to 0.8, a + b + c = 1; −0.1 ≦ e ≦ 0.1) ) And a transition metal oxide having a layer structure of general formula (XI) Li _{1 + t} M _2-t O _4-d (wherein d is 0 to 0.4, and t is 0 to 0.4. And M is Mn and at least one further metal selected from the group consisting of Co and Ni) and Li _{(1 + g)} [Ni _h Co _i Al _j ] _(1-g) O _{2 + k} (g, Standard values for h, I, j and k are: g = 0, h = 0.8-0.85, i = 0.15 to 0.20, j = 0.02 to 0.03 and k = 0).

In one preferred embodiment, the cathode active material is selected from LiCoPO ₄ . A cathode containing LiCoPO ₄ as a cathode active material is also referred to as a LiCoPO ₄ cathode. LiCoPO ₄ is Fe, Mn, Ni, V, Mg, Al, Zr, Nb, Tl, Ti, K, Na, Ca, Si, Sn, Ge, Ga, B, As, Cr, Sr, or a rare earth element, In other words, it may be doped with lanthanides, scandium and yttrium. In particular, LiCoPO ₄ with an olivine structure has a high operating voltage (4.8 V redox potential vs. Li / Li ⁺ ), a flat voltage profile, and a high theoretical capacity of about 170 mAh / g. Is preferred. The cathode may include a LiCoPO ₄ / C composite material. The manufacture of suitable cathodes containing LiCoPO ₄ / C composites is described in Markevich et al. Electrochem. Comm. 2012, 15, 22-25.

In another preferred embodiment of the present invention, the cathode active material has the general formula (X) Li _{(1 + z)} [Ni _a Co _b Mn _c ] _(1-z) O _{2 + e} (wherein z is 0 to 0.00). A, b and c are the same or different and each is 0 to 0.8, and a transition metal oxide having a layer structure of a + b + c = 1; −0.1 ≦ e ≦ 0.1) Selected. Preferably, the general formula (X) Li _{(1 + z)} [Ni _a Co _b Mn _c ] _(1-z) O _{2 + e} (wherein z is 0.05 to 0.3 and a is 0.2 to 0) 0.5, b is 0 to 0.3, c is 0.4 to 0.8, and a transition metal oxide having a layer structure of a + b + c = 1; −0.1 ≦ e ≦ 0.1) It is a thing. In one embodiment of the present invention, the transition metal oxide having a layer structure represented by the general formula (X) includes [Ni _a Co _b Mn _c ] having Ni _0.33 Co ₀ Mn _0.66 and Ni _0.25 Co _0. Mn _0.75, selected from _Ni 0.35 _Co 0.15 _{Mn 0.5,} those selected from Ni _0,21 Co _{0,08 Mn 0,71} and _Ni 0,22 _Co 0,12 _{Mn 0,66} it is, particularly preferably _Ni 0,21 _Co 0,08 _{Mn 0,71} and _Ni 0,22 _Co 0,12 _{Mn 0,66.} Moreover, since the transition metal oxide of general formula (X) is provided with an energy density higher than normal NCMs, it is also called high energy NCM (HE-NCM). Both HE-NCM and NCM have an operating voltage of about 2.3-3.8V versus Li / Li ^+, but to ensure full charge and benefit from its higher energy density, HE -A high cut-off voltage (> 4.6V) must be used for NCMS charging.

According to a further preferred embodiment of the present invention, the cathode active material has the general formula (XI) Li _{1 + t} M _2−t O _{4-d where} d is 0 to 0.4 and t is 0 to 0.4. And M is Mn and at least one further metal selected from the group consisting of Co and Ni). An example of a suitable manganese-containing spinel of the general formula (XI) is LiNi _0,5 Mn _1,5 O _4-d . These spinels are also called HE (high energy) -spinels.

  Many components are ubiquitous. For example, sodium, potassium and chloride can be detected in virtually all inorganic materials in only a very small proportion. In this specification, a proportion of cations or anions of less than 0.5% by weight is ignored, in other words a proportion of cations or anions of less than 0.5% by weight is considered insignificant. Therefore, in this specification, any lithium ion-containing transition metal oxide containing less than 0.5% by weight of sodium is considered sodium free. Correspondingly, in this specification any lithium ion-containing mixed transition metal oxide containing less than 0.5% by weight of sulfate ions is considered sulfuric-free.

  The cathode may further include conventional components such as a conductive material such as conductive carbon and a binder. Compounds suitable as conductive materials and binders are known to those skilled in the art. For example, the cathode may comprise carbon in a conductive polymorph selected from, for example, graphite, carbon black, carbon nanotubes, graphene, or a mixture of at least two of the foregoing materials. In addition, the cathode may include one or more binders such as polyethylene, polyacrylonitrile, polybutadiene, polypropylene, polystyrene, polyacrylate, polyvinyl alcohol, polyisoprene, and ethylene, propylene, styrene, (meth) acrylonitrile and 1,3. A copolymer of at least two comonomers selected from butadiene, in particular ethylene-butadiene copolymer, and polyvinylidene chloride, polyvinyl chloride, polyvinyl fluoride, polyvinylidene fluoride (PVdF), polytetrafluoroethylene, tetrafluoroethylene and One or more organic polymers such as copolymers with hexafluoropropylene, halogenated (co) polymers such as tetrafluoroethylene and vinylidene fluoride and polyacrylonitrile It may also include a.

  Further, the cathode may include a current collector, which may be a metal wire, metal grid, metal web, metal sheet, metal foil or metal plate. The preferred metal foil is aluminum foil.

  According to one embodiment of the invention, the cathode has a thickness of 25 to 200 μm, preferably 30 to 100 μm, based on the total thickness of the cathode without including the thickness of the current collector.

  The anode (C) contained in the lithium ion secondary battery of the present invention contains an anode active material that reversibly occludes and releases lithium ions. In particular, a carbonaceous material capable of reversibly occluding and releasing lithium ions is used as the anode active material. Suitable carbonaceous materials are crystalline carbon such as graphite materials, more particularly natural graphite, graphitized coke, graphitized MCMB and graphitized MPCF, amorphous carbon such as coke, mesocarbon microbeads burned below 1500 ° C. And carbon fibers (MPCF) based on intermediate phases of pitch and hard carbon and carbon anode active materials (carbons to be pyrolyzed, coke, graphite), such as carbon composites, burned organic polymers and carbon fibers is there.

  Further anode active materials are materials containing components that can form lithium metal or alloys with lithium. Non-limiting examples of materials containing components that can form alloys with lithium are metals, metalloids or alloys thereof. As used herein, the term “alloy” should be understood to relate to alloys of two or more metals as well as alloys of one or more metals and one or more metalloids. If the alloy has overall metallic properties, the alloy may contain non-metallic components. In the texture of the alloy, a solid solution, a eutectic material (eutectic mixture), an intermetallic compound, or two or more of them coexist. Examples of such metal or metalloid components are not limited, and titanium (Ti), tin (Sn), lead (Pb), aluminum, indium (In), zinc (Zn), antimony (Sb), bismuth ( Bi), gallium (Ga), germanium (Ge), arsenic (As), silver (Ag), hafnium (Hf), zirconium (Zr), yttrium (Y), and silicon (Si). Preferred are group 4-14 metal and metalloid elements in the elements of the long-period periodic table, and particularly preferred are titanium, silicon and tin, especially silicon. Examples of tin alloys include silicon, magnesium (Mg), nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium, bismuth, antimony and second component elements other than tin. Including those having one or more elements selected from the group consisting of chromium (Cr). Examples of silicon alloys are selected from the group consisting of tin, magnesium, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium as second component elements other than silicon Including those having one or more elements.

A further possible anode active material is silicon capable of storing lithium ions. The silicon is used in various forms, for example nanowires, nanotubes, nanoparticles, films, nanoporous silicon or silicon nanotubes. The silicon may be deposited on a current collector. The current collector may be a metal wire, metal grid, metal web, metal sheet, metal foil or metal plate. A preferred current collector is a metal foil, such as a copper foil. The thin film of silicon may be deposited on the metal foil by any technique known to those skilled in the art (eg, sputtering techniques). One proposal for a Si thin film electrode is R.A. Elazari et al. Electrochem. Comm. (2012), 14 , 21-24. Further, according to the present invention, it is possible to use a silicon / carbon composite as an anode active material.

  Another possible anode active material is an oxide of Ti lithium ion insertion.

  Preferably, the anode active material present in the lithium ion secondary battery of the present invention is selected from carbonaceous materials capable of reversibly occluding and releasing lithium ions, and particularly preferably reversibly occluding and releasing lithium ions. The carbonaceous material which can be selected is selected from crystalline carbon, hard carbon and amorphous carbon, particularly preferably graphite. In another preferred embodiment, the anode active material present in the lithium ion secondary battery of the present invention is selected from silicon capable of reversibly occluding and releasing lithium ions, preferably the anode is silicon or silicon / carbon. Including thin films of composites. In a further preferred embodiment, the anode active material present in the lithium ion secondary battery of the present invention is selected from oxides of lithium ion insertion of Ti.

  The anode and cathode are prepared by dispersing an electrode active material, a binder, and optionally a conductive material and a thickener to produce an electrode slurry composition in a solvent, if necessary, and the slurry composition It is manufactured by a process of applying an object to the surface of the current collector. The current collector may be a metal wire, metal grid, metal web, metal sheet, metal foil or metal plate. Preferably, the current collector is a metal foil, such as a copper foil or an aluminum foil.

  The electrochemical cell of the present invention may include customary additional components such as separators, enclosures, cable connections, and the like. The housing may be any shape, for example, cubic or cylindrical, prismatic, or the housing used is a metal-plastic composite film processed as a pouch. Suitable separators are, for example, polymer separators such as glass fiber separators and polyolefin separators.

  A plurality of electrochemical cells of the present invention may be connected to each other, for example, in series connection or parallel connection. A series connection is preferable. Furthermore, the present invention provides a method of using the electrochemical cell of the present invention in the above apparatus, for example, in a mobile device. Examples of mobile devices include vehicles such as cars, bicycles and aircraft, or water vehicles such as boats or ships. Other examples of mobile devices are portable, for example personal computers, in particular notebook computers, telephones, power tools, such as those from the construction industry, in particular drills, battery-powered screwdrivers or battery-powered nailers. However, the lithium ion battery of the present invention can also be used for stationary energy stores.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

1. Production of compounds of general formula (I) 1a) Lithium bis- (2,2,2-trifluoroethyl) phosphate LiOOP (OCH ₂ CF ₃ ) ₂ (compound 1)
Lithium bis- (2,2,2-trifluoroethyl) phosphate by reacting 8 moles of 2,2,2-trifluoroethanol with 1 mole of P ₄ O ₁₀ (both materials from Alfa Aesar) Manufactured. The reaction product was purified by rectification to give bis- (2,2,2-trifluoroethyl) phosphoric acid in the form of colorless crystals. The acid was dissolved in diethyl ether and cooled, and a slurry of LiH in diethyl ether was added. After evaporating the solvent, white powder lithium bis- (2,2,2-trifluoroethyl) phosphate was obtained.

1b) Lithium bis- (1,1,1,3,3,3-hexafluoroisopropyl) phosphate LiOOP (OCH (CF ₃ ) ₂ ) ₂ (Compound 2)
8 mol of Li [OCH (CF ₃ ) ₂ ] suspension is charged into a mixture of 1 mol of P ₄ O ₁₀ in dimethyl carbonate cooled with ice. The cooling is then removed and the mixture is heated under reflux for 3 hours. Thereafter, the volume of the reaction mixture is reduced by 80% in vacuo. CH ₂ Cl ₂ is added and the mixture is stirred for 4 hours. The white precipitate of LiOOP (OCH (CF ₃ ) ₂ ) ₂ is filtered, washed with cold CH ₂ Cl ₂ and dried in vacuo.

2. Electrolyte composition A 1: 1 volume ratio of a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) and 1M LiPF ₆ or 1M LiBF ₄ was prepared as a comparative example. The mixture containing LiPF ₆ was also used in the production of the gel electrolyte composition of the present invention. Different amounts of lithium bis- (2,2,2-trifluoroethyl) phosphate were added to the LiPF ₆ containing mixture. The mixture was optionally treated for several hours in an ultrasonic bath. Excess solvent was separated by decantation or optionally by centrifugation. In this case, a negligible amount of excess solvent was removed. The above concentrations refer to the sample before separating the excess solvent. All inventive compositions had the appearance of a homogeneous gel.

2a) Conductivity Conductivity was measured at 25 ° C. with a Metrohm SevenMulti electrical conductivity meter equipped with an InLab710 probe. The results are shown in Table 1.

  Example 5 of the present invention showed a lower conductivity than the conductive salt-containing composition, but was a gel.

2b) Rheology Rheology measurements were performed on Example 1 of the present invention at room temperature. A rotary rheometer with a plate-pate geometry with a diameter of 25 mm and a gap of 200 microns was used. The sample was surrounded by silicone oil to avoid sample evaporation. The result of the deformation sweep is shown in FIG. 1, and the result of the oscillation sweep is shown in FIG. G ′ represents an elastic modulus, G ″ represents a loss elastic modulus, γ is a deformation rate, and ω is an angular frequency. As can be seen from FIG. 1 (frequency sweep, storage and loss modulus (pascal) vs. radial frequency (rad / s)) and FIG. 2 (deformation rate sweep, storage and loss modulus (pascal) vs. deformation rate (%)). The electrolyte composition 1 of the present invention exhibits the rheological behavior of a gel.

2c) Cyclic voltammetry Cyclic voltammetry measurement was performed with a Metrohm Autolab PGStat 101 equipped with a platinum working electrode (diameter 1 mm) and a working and reference electrode made of lithium foil. The scan rate was set to 10 mV per second. The electrolyte consisted of 1 mol / L Li [PF ₆ ] in EC / DMC (1: 1) mixed with 1 mol / L LiOOP (OCH ₂ CF ₃ ) ₂ . The results are shown in FIGS. 3 and 4 (cyclic voltammograms of LiOOP (OCH ₂ CF ₃ ) ₂ in 1 mol / L Li [PF ₆ ] in EC / DMC (1: 1)).

2d) lithium-nickel-cobalt-manganese oxide having a capacitance of performance test 2mAh / cm ² (NCM111) with graphite electrodes having a capacitance of the electrode and 2.15mAh / cm ^2, were assembled button cell. A glass fiber filter separator (Whatmann GF / D) was used as the separator. The separator was immersed in 100 μl of electrolyte. The electrode consisted of 1 mol / L Li [PF ₆ ] in EC / DMC (1: 1) mixed with 0.235 mol / L LiOOP ₂ (OCH ₂ CF ₃ ) ₂ . All electrochemical measurements were performed in an artificial climate room at 25 ° C. According to the procedure shown in Table 2, the performance of the battery with respect to the number of cycles was measured.

The specific capacity of an electrolyte composed of 1 mol / L Li [PF ₆ ] in EC / DMC (1: 1) mixed with 0.235 mol / L LiOOP ₂ (OCH ₂ CF ₃ ) ₂ according to the number of cycles. In FIG. 5, hollow triangles represent the specific capacitance during charging, and full triangles represent the specific capacitance during discharge.

FIG. 1 shows the result of a deformation sweep during rheology measurement. FIG. 2 shows the results of a vibration sweep during rheology measurement. FIG. 3 shows the results of cyclic voltammetry measurement. FIG. 4 shows the results of cyclic voltammetry measurement. FIG. 5 shows the specific capacitance of the electrolyte according to the number of cycles.

Claims (6)

Formula (I),

Wherein R ¹ and R ² are independently of each other selected from C ₁ -C ₄ -alkyl, which can be substituted by one or more F , wherein at least one of R ¹ and R ² is at least Substituted with 3 F )
The compounds, cyclic and at least one aprotic organic solvent Nakadachimata selected from acyclic organic carbonate is a solvent mixture, compounds of general formula (I), at least one of the general formula (I) Conductive salts different from the compounds and further additives
How to use as a gelling agent in the electrolyte composition comprising. Compounds of general formula (I), at least one of R ¹ and R ² at least one CF 3 _- is selected from the compounds of general formula (I) containing a group, Use according to claim 1 . Compounds of general formula _{(I), LiOOP (OCH 2 CF 3)} 2, LiOOP (OCH (CF 3) 2) 2, LiOOP (On-C 4 F 9) 2 and LiOOP (OC _{(CF 3)} 3 The method according to any one of claims 1 and 2 , wherein the method is selected from ₂ . Based on the total volume of the composition containing the aprotic organic solvent (s) and the compound (s) of the general formula (I) from 0.01 to 5 mol / L is used in a concentration ranging, use according to any one of claims 1-3. The method according to any one of claims 1 to 4 , wherein the aprotic organic solvent contains at least one conductive salt. By reacting LiOR ¹ , LiOR ² and / or LiOR ¹ R ² OLi with phosphorus pentoxide, the general formula (I),

Wherein R ¹ and R ² are independently of each other selected from C ₁ -C ₄ -alkyl, which can be substituted with one or more F, wherein at least one of R ¹ and R ² is at least Substituted with 3 F )
The method of manufacturing the compound of this.

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